The method of preparation aluminoborosilicate catalyst hydrotreating petroleum fractions

 

(57) Abstract:

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating of various petroleum fractions, and can be used in the refining industry. Describes the method of preparation aluminoborosilicate catalyst Hydrotreating petroleum fractions, including deposition of aluminum hydroxide, the introduction of aluminum hydroxide salts of molybdenum and cobalt, molding, extrusion, drying and calcination, and fractional two-stage peptization aluminum hydroxide with a humidity of 75-85 wt. % hold first nitric acid taken in the quantity of 0,005-0,010 mol/mol Al2ABOUT3with the subsequent introduction in patinirovannuyu mass of salts of molybdenum and cobalt, mixing and evaporation to a humidity of 70-72 wt.%, and then re-peptization spend monobasic organic acid in an amount of 0.004-0,0275 mol/mol Al2ABOUT3after the implementation of subsequent stages - forming, drying and annealing gives a catalyst with a homogeneous size distribution of the pore radii, 60-80% of which are pores with a radius of 20-70 . Technical result: obtaining a catalyst with increased active the e refers to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating of various petroleum fractions, and can be used in the oil industry.

The aim of the invention is the preparation of a catalyst with increased activity and higher performance characteristics, to obtain the catalyst with a homogeneous porous structure, 60-80% of the pores of which are pores with a radius of 20-70 due to the two-stage fractional peptization, intended for the preparation of aluminum hydroxide for introduction into the composition of the salts of molybdenum and cobalt and preparation of a catalyst mass for molding.

The prior art consists in the following: the known methods of preparation aluminoborosilicate Hydrotreating catalysts by the method of co-extrusion of aluminum hydroxide (boehmite) with aqueous solutions of salts of cobalt and molybdenum or an aqueous solution of salt of one of the metals, followed by drying, calcination and impregnation with an aqueous solution of the salt of the second metal (Nefedov B. K., Radchenko, E. D. , Aliyev P. P. Catalysts processes deep oil processing. - M.: Chemistry, 1999, S. 144).

The disadvantage of these methods is low gidroobesserivaniya activity - the degree of desulfurization with whom the playing technique is a method (U.S. Pat. R. F. 2073566, 20.02.97, C1, B 01 J 37/02, 23/882). The disadvantages of this method are low gidroobesserivaniya activity - the degree of desulfurization of the raw materials does not exceed 93 Rel.%, and low mechanical strength, especially for catalysts with highly developed internal surface.

The invention consists in the following: the invention is directed to solving the problem of preparation of highly active catalyst for Hydrotreating petroleum fractions with high mechanical strength along with highly developed internal surface area and uniform pore size distribution along the radius, 60-80% of which are pores with a radius of 20-70 .

The technical result allows us to solve the task and is achieved by the method of preparation of the catalyst, including the precipitation of aluminium hydroxide, the introduction of aluminum hydroxide salts of molybdenum and cobalt, molding, extrusion, drying and calcination, wherein the fractional two-stage peptization aluminum hydroxide with a humidity of 75-85 wt. % hold first nitric acid taken in the quantity of 0,005-0,010 mol per mol of Al2ABOUT3with the subsequent introduction in patinirovannuyu mass of salts of molybdenum and cobalt acid in an amount of 0.004-0,0275 mol per mol of Al2ABOUT3with the receipt of aluminum hydroxide-modified compounds of molybdenum and cobalt with a dense packing of particles, which allows for subsequent stages - forming, extrusion, drying and calcination to obtain a catalyst with a homogeneous size distribution of the pore radii, 60-80% of which are pores with a radius of 20-70 .

Distinctive features of the present invention is a method for preparing aluminoborosilicate catalyst Hydrotreating petroleum fractions, including the introduction of salts of molybdenum and cobalt in the mass of aluminum hydroxide with a humidity of 75-85 wt.%, pre patinirovannuyu nitric acid taken in the quantity of 0,005-0,010 mol per mol of Al2ABOUT3with subsequent evaporation of the mass to a moisture content 70-72 wt.% and re-processing catalyst weight monobasic organic acid in an amount of 0.004-0,0275 mol per mol of Al2ABOUT3with the receipt of aluminum hydroxide-modified compounds of molybdenum and cobalt with a dense packing of particles, which allows for the subsequent stages of production of the catalyst - forming, drying, calcination to obtain the catalyst, 60-80% of the pore volume is in pores with a radius of 20-70 .

the composition of salts of molybdenum and cobalt - this is bringing the aluminum hydroxide to a moisture content of 75 to 85 wt.% and fractional two-stage peptidase its nitric acid taken in the quantity of 0,005-0,010 mol per mol of Al2ABOUT3and the method of preparation of a catalyst mass for molding is bringing the catalyst mass to a moisture content 70-72 wt.%, then peptidase her monobasic organic acid, taken in an amount of 0.004-0,0275 mol per mol A12ABOUT3with the receipt of aluminum hydroxide-modified molybdenum and cobalt, with a dense packing of particles. The presence of these stages of preparation of the catalyst promotes a uniform distribution of the active phase of the catalyst and to obtain a catalyst with a highly developed internal surface with a uniform pore size distribution, 60-80% of which are pores with a radius of 20-70 , along with its high mechanical strength, which leads to increased gidroobesserivaniya activity aluminoborosilicate catalyst Hydrotreating petroleum fractions.

The invention is illustrated by the following examples.

Example 1

In the mixer load of 325 kg of aluminum hydroxide obtained by presidenial of three-hydrate of aluminum oxide with a humidity of 75 wt.%, peptizer 300 ml of 60% is lenovolenovo and 14.8 kg of cobalt nitrate, mix with simultaneous evaporation mass to a moisture content of 70 wt.% and treated with 200 ml of glacial acetic acid, which corresponds to 0.0004 mole of CH3COOH. The obtained catalyst mass is evaporated to a moisture content of 55-60 wt.%, required for forming by extrusion, molded by extrusion, dried in the temperature range from 60 to 120oC and calcined at a temperature of 550oC.

The resulting catalyst has the following chemical composition: Moo3=12 wt.%; Soo= 4 wt.%; Al2ABOUT3=84 wt.% and is characterized by the following porous structure Rthen=60-70 , the proportion of pores with a given radius of 60-70%.

Example 2

In the mixer load of 325 kg of aluminum hydroxide obtained by presidenial of three-hydrate of aluminum oxide with a humidity of 80 wt.%, peptizer 600 ml of 60% nitric acid, which corresponds 0,010 mol NGO3on mol Al2ABOUT3, fall asleep 11,9 kg of ammonium molybdate and 12.0 kg of cobalt nitrate, mix with simultaneous evaporation mass to a moisture content of 71 wt.% and treated with 400 ml of glacial acetic acid, which is 0,010 mol of CH3COOH. The obtained catalyst mass evaporated, molded, dried and calcined as in example 1. The catalyst is followed by the radius - 70-75%.

Example 3

In the mixer load of 325 kg of aluminum hydroxide obtained by presidenial of three-hydrate of aluminum oxide with a humidity of 85 wt.%, peptizer 900 ml of 60% nitric acid, which corresponds to 0,024 mole NGO3on mol Al2ABOUT3, fall asleep 9,0 kg of ammonium molybdate and 9.1 kg of cobalt nitrate, mix with simultaneous evaporation mass to a moisture content of 70 wt.% and treated with 600 ml of glacial acetic acid, which corresponds to at 0.020 mol of CH3COOH. The obtained catalyst mass is evaporated to a moisture content of 55-60 wt.%, required for forming by extrusion, molded by extrusion, dried in the temperature range from 60 to 120oC and calcined at a temperature of 550oC.

The resulting catalyst has the following chemical composition: Moo3=12 wt.%; Soo= 4 wt. %; Al2ABOUT3= 84 wt.%, Rthen=20-30 , the proportion of pores with a given radius is 75-80%.

Example 4

In the mixer load of 325 kg of aluminum hydroxide obtained by presidenial of three-hydrate of aluminum oxide with a humidity of 85 wt.%, peptizer 900 ml of 60% nitric acid, which corresponds to 0.025 mole NGO3on mol Al2ABOUT3, fall asleep 9,0 kg of ammonium molybdate and 9.1 kg of cobalt nitrate, paremata corresponds 0,026 mol of CH3COOH. The obtained catalyst mass is molded, dried and calcined as in example 1. The resulting catalyst has the following chemical composition: Moo3= 12 wt.%; Soo=4 wt.%; Al2ABOUT3=84 wt.%, Rthen=20-30 , the proportion of pores with a given radius is 75-80%.

Physico-chemical properties of the synthesized catalysts and the results of their testing in the Hydrotreating process high-sulfur diesel fuel with a sulfur content of 0.92 wt.% on running the installation under hydrogen pressure of 3 MPa, the space velocity of the raw material 4 h-1the ratio of hydrogen to the raw material - 400 nl/l and temperatures of 340 and 380oPresented in table and figure. For comparison, table and figure shows the data for testing and the properties of the underlying domestic Hydrotreating catalyst AKM and catalyst of the prototype.

The method of preparation aluminoborosilicate catalyst Hydrotreating petroleum fractions, including deposition of aluminum hydroxide, peptization aluminum hydroxide with nitric acid, the introduction of aluminum hydroxide salts of molybdenum and cobalt, molding, extrusion, drying and calcination, wherein spend fractional two-stage peptization first hydroxide of aluminide in patinirovannuyu mass of salts of molybdenum and cobalt, mixing and evaporation to a humidity of 70-72 wt. %, re peptization monobasic organic acid in an amount of 0.004-0,0275 mol/mol Al2ABOUT3after the implementation of subsequent stages of forming, drying, annealing gives a catalyst with uniform distribution of the pore radii, 60-80% of which are pores with a radius of 20-70 .

 

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FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

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